U.S. patent application number 17/236524 was filed with the patent office on 2021-08-26 for coating liquid used for forming ultraviolet absorption coating and ultraviolet absorption glass.
The applicant listed for this patent is Fuyao Glass Industry Group Co., Ltd. Invention is credited to Wenhui CHEN, Shanji GUO, Bingming JIANG, Cheng KE, Zhonghua ZHOU.
Application Number | 20210261798 17/236524 |
Document ID | / |
Family ID | 1000005568177 |
Filed Date | 2021-08-26 |
United States Patent
Application |
20210261798 |
Kind Code |
A1 |
ZHOU; Zhonghua ; et
al. |
August 26, 2021 |
Coating Liquid Used For Forming Ultraviolet Absorption Coating And
Ultraviolet Absorption Glass
Abstract
Provided is an ultraviolet absorption glass comprising: a glass
substrate, and an ultraviolet absorption coating arranged on at
least one surface of the glass substrate, wherein the ultraviolet
absorption coating comprises silicon dioxide, an ultraviolet
absorber, and MOz used for storing and releasing electrons excited
by ultraviolet light in the ultraviolet absorber. The ultraviolet
absorption glass is low cost and has good resistance to
discoloration and devitrification.
Inventors: |
ZHOU; Zhonghua; (Fuzhou,
CN) ; GUO; Shanji; (Fuzhou, CN) ; KE;
Cheng; (Fuzhou, CN) ; CHEN; Wenhui; (Fuzhou,
CN) ; JIANG; Bingming; (Fuzhou, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Fuyao Glass Industry Group Co., Ltd |
Fuzhou |
|
CN |
|
|
Family ID: |
1000005568177 |
Appl. No.: |
17/236524 |
Filed: |
April 21, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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15038282 |
May 20, 2016 |
11015068 |
|
|
PCT/CN2014/083016 |
Jul 25, 2014 |
|
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17236524 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 27/00 20130101;
Y10T 428/31663 20150401; C09D 183/04 20130101; B32B 2383/00
20130101; C09D 5/32 20130101; B32B 17/10678 20130101; B32B 27/283
20130101 |
International
Class: |
C09D 5/32 20060101
C09D005/32 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 22, 2013 |
CN |
201310597206.2 |
Claims
1. An ultraviolet absorption glass comprising: a glass substrate,
and an ultraviolet absorption coating arranged on at least one
surface of the glass substrate, wherein the ultraviolet absorption
coating comprises silicon dioxide, an ultraviolet absorber, and MOz
used for storing and releasing electrons excited by ultraviolet
light in the ultraviolet absorber, and wherein MOz is at least one
compound selected from the group consisting of VO.sub.5/2,
MnO.sub.2, FeO.sub.3/2, CoO.sub.4/3, NiO, YO.sub.3/2, ZrO.sub.2,
NbO.sub.5/2, MoO.sub.3, RuO.sub.2, RhO.sub.3/2, PdO, TaO.sub.5/2,
WO.sub.3, ReO.sub.3, OsO.sub.4, IrO.sub.2, GaO.sub.3/2,
InO.sub.3/2, SnO.sub.2, SbO.sub.5/2 and BiO.sub.5/2.
2. The ultraviolet absorption glass according to claim 1, wherein
in the ultraviolet absorption coating, a molar ratio of MOz to
silicon dioxide is in a range of 1/300-1/100.
3. The ultraviolet absorption glass according to claim 2, wherein
in the ultraviolet absorption coating, a molar ratio of MOz to
silicon dioxide is in a range of 1/180-1/120.
4. The ultraviolet absorption glass according to claim 1, wherein
in the ultraviolet absorption coating, a molar ratio of MOz to
ultraviolet absorber is in a range of 1/20-1/10.
5. The ultraviolet absorption glass according to claim 4, wherein
in the ultraviolet absorption coating, a molar ratio of MOz to
ultraviolet absorber is in a range of 1/18-1/12.
6. The ultraviolet absorption glass according to claim 1, wherein a
color difference between the ultraviolet absorption glass and the
glass substrate is in a range of .DELTA.E*ab.ltoreq.2.0.
7. The ultraviolet absorption glass according to claim 1, wherein
the ultraviolet absorber is benzophenone ultraviolet absorber,
benzimidazole ultraviolet absorber or triazine ultraviolet
absorber.
8. The ultraviolet absorption glass according to claim 1, wherein
the ultraviolet absorption coating further comprises H.sup.+ or an
alkali metal ion.
9. The ultraviolet absorption glass according to claim 1, wherein
the ultraviolet absorption coating is formed by drying a coating
liquid at a temperature between 100.degree. C. and 200.degree.
C.
10. The ultraviolet absorption glass according to claim 9, wherein
the coating liquid comprises partially hydrolyzed condensates of a
silane compound, an ultraviolet absorber, a precursor of MOz,
deionized water and at least one alcohol, and wherein the precursor
is soluble in deionized water and/or the alcohol to produce
MOz.
11. The ultraviolet absorption glass according to claim 10, wherein
the precursor is at least one compound selected from the group
consisting of LiVO.sub.3, HMnO.sub.4, Na.sub.2FeO.sub.4,
Li.sub.2MoO.sub.4, H.sub.2RuO.sub.4, Na.sub.2WO.sub.4,
H.sub.2ReO.sub.4, K.sub.2OsO.sub.4, NaGaO.sub.2,
Na.sub.2SnO.sub.3.
12. The ultraviolet absorption glass according to claim 10, wherein
the alcohol is selected from ethanol and isopropanol.
13. The ultraviolet absorption glass according to claim 1, wherein
the glass substrate is a green float glass.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a divisional application of No.
U.S. Ser. No. 15/038,282, filed on May 20, 2016, which claims
priority to PCT application no. PCT/CN2014/083016, filed on Jul.
25, 2014, which claims priority to Chinese Patent Application No.
201310597206.2, filed on Nov. 22, 2013, the disclosures of which
are hereby incorporated by reference in their entireties.
TECHNICAL FIELD
[0002] The present invention relates to the technical field of
ultraviolet absorption coating, particularly to a coating liquid
used for forming an ultraviolet absorption coating on a surface of
an object such as glass and the like, and an ultraviolet absorption
glass arranged with the ultraviolet absorption coating formed by
the coating liquid. Furthermore, a method for preparing the
ultraviolet absorption glass is provided.
BACKGROUND
[0003] Due to environmental pollution brought by industrial
development, atmospheric ozonosphere suffers from more and more
serious impact. Moreover, more and more ultraviolet rays in
sunlight radiate to ground. As we all know, long-time ultraviolet
irradiation harms people's health, such as wrinkles and spots due
to skin aging, rough skin or dermatitis and even skin cancer;
moreover, it will also result in aging and color fading of
automotive trim and house interior decorations in a short time and
finally influence people's use. In order to reduce harm of
ultraviolet to people's health and influence on people's life, for
a long time, people keep on developing automotive glass or building
glass which can absorb or reflect ultraviolet rays.
[0004] In the prior art, rare earth elements can be added to a
glass substrate. Thus, the glass substrate can absorb ultraviolet
rays. For example, Chinese Patent CN1089730(C) discloses a green
glass composite absorbing infrared and ultraviolet radiation.
Cerium dioxide (CeO.sub.2) is added to the green glass composite.
CeO.sub.2 is a strong ultraviolet absorber and basically gives no
color to the glass. However, as it is a rare earth element, and is
added in the preparing process, the manufacturing cost of glass
substrate is enhanced.
[0005] Moreover, ultraviolet absorber can be added in the
intermediate membrane of laminated glass in order to enable the
glass absorbing ultraviolet. For example, Chinese Patent
CN103097320 (A) discloses a laminated glass intermediate membrane.
An ultraviolet absorber added in the membrane makes the laminated
glass able to absorb ultraviolet. However, as at least two glass
substrates and one ultraviolet absorbing intermediate membrane are
needed, the manufacturing process is complicated, and the cost is
relatively high; moreover, as only the intermediate membrane can
absorb ultraviolet, it can only be manufactured into laminated
glass. Due to high cost, laminated glass is only used as
windscreen. Side window glass of vehicles is usually made of
single-layer tempered glass. Therefore, application range of this
method is small.
[0006] Another solution is to apply an ultraviolet absorption
coating on surface of a glass substrate to prepare an ultraviolet
absorption glass. This method applies to both laminated glass and
single-layer glass. For example, Chinese Patent CN102892851(A)
discloses a coating liquid for formation of ultraviolet absorption
film and an ultraviolet absorption glass product. By applying
ultraviolet absorption coating liquid on surface of glass
substrate, an ultraviolet absorption film is formed. The coating
liquid contains silicon oxide matrix components and ultraviolet
absorber. Though the film is able to absorb ultraviolet and has
high abrasion resistance and mechanical endurance. However, in
practical application, the ultraviolet absorption film is easy to
discolor or devitrify, which results in discoloration or
devitrification, weak weather resistance, even a yellow appearance
of a part of the ultraviolet absorption glass.
[0007] Similarly, Chinese Patent CN102421862A discloses a coating
liquid for formation of ultraviolet absorption film and an
ultraviolet absorption glass product. The coating liquid comprises
a combination of the following three components: a component
derived from an epoxidized organooxysilane compound (a), a
component derived from an organooxysilane compound (b) which is a
reaction product of a hydroxylated benzophenone compound and an
epoxidized organooxysilane compound, and a component derived from
an organooxysilane compound (c) other than the above (a) and (b),
wherein each of the above three components is the corresponding
organooxysilane compound of the above (a), (b) or (c), or a
constituting component of a partially hydrolyzed condensate of at
least the corresponding organooxysilane compound of the above (a),
(b) or (c). Though the ultraviolet absorption film is capable to
absorb ultraviolet and has high abrasion resistance and mechanical
endurance, in practical applications, the ultraviolet absorption
film is easy to discolor or devitrify, which results in
discoloration or devitrification, weak weather resistance, even a
yellow appearance of a part of the ultraviolet absorption
glass.
SUMMARY
[0008] The technical problem to be solved is to overcome the
shortages of an existing ultraviolet absorption glass, including
high cost, a high tendency towards discoloration or devitrification
and poor weather resistance. The present invention provides a
coating liquid used for forming ultraviolet absorption coating, and
an ultraviolet absorption glass arranged with the ultraviolet
absorption coating formed by the coating liquid. Furthermore, a
method for preparing the ultraviolet absorption glass is
provided.
[0009] A technical solution provided in the present invention to
solve the technical problem is: a coating liquid used for forming
ultraviolet absorption coating, comprising partially hydrolyzed
condensates of a silane compound and an ultraviolet absorber,
wherein the coating liquid further comprises AxMOy where A is
hydrogen or alkali metal, O is oxygen, M is at least one element
selected from the group consisting of vanadium, manganese, iron,
cobalt, nickel, yttrium, zirconium, niobium, molybdenum, ruthenium,
rhodium, palladium, tantalum, tungsten, rhenium, osmium, iridium,
gallium, indium, stannum, antimony and bismuth, x is in a range of
1.ltoreq.x.ltoreq.2, y is in a range of 1.ltoreq.y.ltoreq.4.
[0010] Furthermore, the silane compound is at least one compound
selected from the group consisting of tetramethoxysilane,
tetraethoxysilane, trimethoxysilane, triethoxysilane and
dimethoxydimethylsilane.
[0011] Furthermore, the coating liquid further comprises deionized
water and at least one alcohol.
[0012] Furthermore, the alcohol in the coating liquid is ethanol
and isopropanol.
[0013] Furthermore, the coating liquid further comprises a silane
additive.
[0014] Furthermore, the silane additive is at least one compound
selected from the group consisting of
N-[3-(trimethoxysilyl)propyl]ethylenediamine,
[3-(methacryloyloxy)propyl] trimethoxysilane,
[3-(2-aminoethyl)aminopropyl]trimethoxysilane and
[3-(methacryloyloxy)propyl] triethoxysilane.
[0015] Furthermore, the AxMOy is at least one compound selected
from the group consisting of LiVO.sub.3, HMnO.sub.4,
Na.sub.2FeO.sub.4, LiCoO.sub.2, LiNiO.sub.2, NaYO.sub.2,
Na.sub.2ZrO.sub.3, LiNbO.sub.3, Li.sub.2MoO.sub.4,
H.sub.2RuO.sub.4, LiRhO.sub.2, Li.sub.2PdO.sub.3, LiTaO.sub.3,
Na.sub.2WO.sub.4, H.sub.2ReO.sub.4, K.sub.2OsO.sub.4, KIrO.sub.3,
NaGaO.sub.2, NaInO.sub.2, Na.sub.2SnO.sub.3, NaSbO.sub.3 and
NaBiO.sub.3.
[0016] Furthermore, the ultraviolet absorber is benzophenone
ultraviolet absorber, benzimidazole ultraviolet absorber or
triazine ultraviolet absorber.
[0017] In addition, the present invention further provides an
ultraviolet absorption glass comprising a glass substrate and an
ultraviolet absorption coating formed by a coating liquid, the
ultraviolet absorption coating being arranged on at least one
surface of the glass substrate, the ultraviolet absorption coating
comprising silicon dioxide and an ultraviolet absorber, wherein the
ultraviolet absorption coating further comprises MOz used for
storing and releasing electrons that excited by ultraviolet lights
in the ultraviolet absorber, where O is oxygen, M is at least one
element selected from the group consisting of vanadium, manganese,
iron, cobalt, nickel, yttrium, zirconium, niobium, molybdenum,
ruthenium, rhodium, palladium, tantalum, tungsten, rhenium, osmium,
iridium, gallium, indium, stannum, antimony and bismuth, z is in a
range of 1.ltoreq.z.ltoreq.4.
[0018] Furthermore, the MOz is at least one compound selected from
the group consisting of VO.sub.5/2, MnO.sub.2, FeO.sub.3/2,
CoO.sub.4/3, NiO, YO.sub.3/2, ZrO.sub.2, NbO.sub.5/2, MoO.sub.3,
RuO.sub.2, RhO.sub.3/2, PdO, TaO.sub.5/2, WO.sub.3, ReO.sub.3,
OsO.sub.4, IrO.sub.2, GaO.sub.3/2, InO.sub.3/2, SnO.sub.2,
SbO.sub.5/2 and BiO.sub.5/2.
[0019] Furthermore, the ultraviolet absorber is benzophenone
ultraviolet absorber, benzimidazole ultraviolet absorber or
triazine ultraviolet absorber.
[0020] Furthermore, in the ultraviolet absorption coating, a molar
ratio of MOz to silicon dioxide is in a range of 1/300-1/100.
[0021] Further, in the ultraviolet absorption coating, a molar
ratio of MOz to silicon dioxide is in a range of 1/180-1/120.
[0022] Furthermore, in the ultraviolet absorption coating, a molar
ratio of MOz to ultraviolet absorber is in a range of
1/20-1/10.
[0023] Further, in the ultraviolet absorption coating, a molar
ratio of MOz to ultraviolet absorber is in a range of
1/18-1/12.
[0024] Furthermore, the glass substrate is a white float glass or a
green float glass.
[0025] Furthermore, a color difference between the ultraviolet
absorption glass and the glass substrate is in a range of
.DELTA.E*ab.ltoreq.2.0.
[0026] Furthermore, the present invention also provides a method
for preparing an ultraviolet absorption glass, comprising the steps
of:
[0027] step 1: providing silane compound and AxMOy as raw material,
providing deionized water and at least one alcohol as a solvent,
stirring and ultrasonically dispersing the raw material and
solvent, wherein A is hydrogen or alkali metal, O is oxygen, M is
at least one element selected from the group consisting of
vanadium, manganese, iron, cobalt, nickel, yttrium, zirconium,
niobium, molybdenum, ruthenium, rhodium, palladium, tantalum,
tungsten, rhenium, osmium, iridium, gallium, indium, stannum,
antimony and bismuth, x is in a range of 1.ltoreq.x.ltoreq.2, y is
in a range of 1.ltoreq.y.ltoreq.4;
[0028] step 2: after the step of stirring and ultrasonically
dispersing, conducting a hydrolysis reaction and a condensation
reaction between the raw material and solvent to produce a colloid
B containing silicon dioxide in a form of a partially hydrolyzed
condensate;
[0029] step 3: adding an ultraviolet absorber and a silane additive
to the colloid B while stirring to dissolve the ultraviolet
absorber, then obtaining a coating liquid C used for forming an
ultraviolet absorption coating;
[0030] step 4: preparing a glass substrate, applying the coating
liquid C uniformly on at least one surface of the glass
substrate;
[0031] step 5: drying the coating liquid C at a temperature of
100.degree. C.-200.degree. C. to form an ultraviolet absorption
coating containing MOz on a surface of the glass substrate, O is
oxygen, M is at least one element selected from the group
consisting of vanadium, manganese, iron, cobalt, nickel, yttrium,
zirconium, niobium, molybdenum, ruthenium, rhodium, palladium,
tantalum, tungsten, rhenium, osmium, iridium, gallium, indium,
stannum, antimony and bismuth, z is in a range of
1.ltoreq.z.ltoreq.4, thereby obtaining an ultraviolet absorption
glass.
[0032] Furthermore, the silane compound is at least one compound
selected from the group consisting of tetramethoxysilane,
tetraethoxysilane, trimethoxysilane, triethoxysilane and
dimethoxydimethylsilane.
[0033] Furthermore, the alcohol in step 1 is ethanol and
isopropanol.
[0034] Furthermore, the AxMOy in step 1 is at least one compound
selected from the group consisting of LiVO.sub.3, HMnO.sub.4,
Na.sub.2FeO.sub.4, LiCoO.sub.2, LiNiO.sub.2, NaYO.sub.2,
Na.sub.2ZrO.sub.3, LiNbO.sub.3, Li.sub.2MoO.sub.4,
H.sub.2RuO.sub.4, LiRhO.sub.2, Li.sub.2PdO.sub.3, LiTaO.sub.3,
Na.sub.2WO.sub.4, H.sub.2ReO.sub.4, K.sub.2OsO.sub.4, KIrO.sub.3,
NaGaO.sub.2, NaInO.sub.2, Na.sub.2SnO.sub.3, NaSbO.sub.3 and
NaBiO.sub.3.
[0035] Furthermore, the silane additive in step 3 is at least one
compound selected from the group consisting of
N-[3-(trimethoxysilyl)propyl]ethylenediamine,
[3-(methacryloyloxy)propyl] trimethoxysilane,
[3-(2-aminoethyl)aminopropyl]trimethoxysilane and
[3-(methacryloyloxy)propyl] triethoxysilane.
[0036] Furthermore, the MOz in step 5 is at least one compound
selected from the group consisting of VO.sub.5/2, MnO.sub.2,
FeO.sub.3/2, CoO.sub.4/3, NiO, YO.sub.3/2, ZrO.sub.2, NbO.sub.5/2,
MoO.sub.3, RuO.sub.2, RhO.sub.3/2, PdO, TaO.sub.5/2, WO.sub.3,
ReO.sub.3, OsO.sub.4, IrO.sub.2, GaO.sub.3/2, InO.sub.3/2,
SnO.sub.2, SbO.sub.5/2 and BiO.sub.5/2.
[0037] Furthermore, the step of drying the coating liquid C in step
5 is conducted for 30 to 120 minutes.
[0038] Furthermore, the ultraviolet absorber is benzophenone
ultraviolet absorber, benzimidazole ultraviolet absorber or
triazine ultraviolet absorber.
[0039] With the above technical solutions, the present invention
has beneficial effects as described below.
[0040] The present invention provides a coating liquid used for
forming the ultraviolet absorption coating, an ultraviolet
absorption glass and a method for preparing the ultraviolet
absorption glass. By storing and releasing electrons excited by
ultraviolet lights in an ultraviolet absorber, the present
invention reduces the excited electrons that are gradually
accumulated during a process in which the ultraviolet absorber
absorbs the ultraviolet lights, thus protecting the ultraviolet
absorber and a silicon dioxide matrix, preventing the ultraviolet
absorption glass from discoloring or devitrifying, ensuring weather
resistance of the ultraviolet absorption coating and ensuring color
consistency of the ultraviolet absorption glass.
BRIEF DESCRIPTION OF THE DRAWINGS
[0041] FIG. 1 shows an ultraviolet absorption glass of the present
invention, where element 1 is a glass substrate, and element 2 is
an ultraviolet absorption coating.
DETAILED DESCRIPTION
[0042] Further description of the present invention will be
illustrated, which combined with embodiments in the drawings.
[0043] The coating liquid used for forming ultraviolet absorption
coating of the present invention comprises partially hydrolyzed
condensates of a silane compound and an ultraviolet absorber. The
partially hydrolyzed condensates of a silane compound contain
silicon dioxide, which can be used for improving hardness and
adhesion to the glass substrate of the ultraviolet absorption
coating which is formed by the coating liquid, thereby ensuring
high durability of the ultraviolet absorption coating. An
ultraviolet absorber absorbs ultraviolet (UV) light and blocks the
UV light coming into the vehicle or the house, avoiding damage to
human health and aging of the decoration.
[0044] The term "partially hydrolyzed condensates" refers to
oligomers (polymers) generated by hydrolysis and
dehydration-condensation of an organic silane compound, which is
generally polymerizing and dissolved in a solvent to an extent. The
partially hydrolyzed condensates containing organic oxy group or
silanol group are able to hydrolysis and condensate further to give
final substance. The silane compound is at least one compound
selected from the group consisting of tetramethoxysilane,
tetraethoxysilane, trimethoxysilane, triethoxysilane and
dimethoxydimethylsilane. In general, a single silane compound
produces partially hydrolyzed condensates, while two or more silane
compounds produce partial hydrolyzed co-condensates as their
co-condensates. They are collectively referred to as "partially
hydrolyzed condensate" in the present invention.
[0045] It is well known in the prior art that an ultraviolet
absorption glass containing a surface coating of silicon dioxide
(SiO.sub.2) and ultraviolet absorber absorbs the ultraviolet light.
However, after being used for a period of time, the surface coating
tends to become discolored or devitrified, resulting in
discoloration or devitrification of the ultraviolet absorption
glass, even a yellow appearance of a part of the glass. After
absorbing the ultraviolet light, outer electrons of the ultraviolet
absorber molecule jump from the ground state to an excited state
(anti-bonding orbital), being raised to an excited state. The
excited electrons can not be transferred. When the excited
electrons accumulate and reach the capacity of ultraviolet absorber
molecule, ultraviolet absorber or silicon dioxide will be
destroyed, leading to discoloration or devitrification and a yellow
appearance of the glass. Actually, such ultraviolet absorption
glass has poor weather resistance in practical use. Therefore, the
coating liquid used for forming ultraviolet absorption coating of
the present invention further comprises AxMOy, where A is hydrogen
or alkali metal, O is oxygen, M is at least one element selected
from the group consisting of vanadium (V), manganese (Mn), iron
(Fe), cobalt (Co), nickel (Ni), yttrium (Y), zirconium (Zr),
niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh),
palladium (Pd), tantalum (Ta), tungsten (W), rhenium (Re), osmium
(Os), iridium (Ir), gallium (Ga), indium (In), stannum (Sn),
antimony (Sb) and bismuth (Bi), x is in a range of
1.ltoreq.x.ltoreq.2, y is in a range of 1.ltoreq.y.ltoreq.4. The
MOz is used for storing and releasing electrons that excited by
ultraviolet lights in the ultraviolet absorber.
[0046] Further, the coating liquid used for forming ultraviolet
absorption coating further comprises deionized water and at least
one of alcohol as solvent. Preferably, the alcohol in the coating
liquid is ethanol and isopropanol, since both of the two alcohols
are capable of dissolving the ultraviolet absorber and have a lower
boiling point.
[0047] In addition, the coating liquid used for forming ultraviolet
absorption coating further comprises a silane additive which is
capable of improving adhesion of the coating liquid to the glass
substrate. The silane additive is at least one compound selected
from the group consisting of
N-[3-(trimethoxysilyl)propyl]ethylenediamine,
[3-(methacryloyloxy)propyl]trimethoxysilane,
[3-(2-aminoethyl)aminopropyl]trimethoxysilane and
[3-(methacryloyloxy)propyl]triethoxysilane. These silane additives
can be purchased commercially, such KH470 (Nanjing Shuguang
Company), KH560 (Nanjing Shuguang Company), KBM603 (Shin-Etsu
Chemicals) or A1120 (Momentive Chemicals), etc.
[0048] In practical applications, the AxMOy is preferably at least
one compound selected from the group consisting of lithium vanadate
(LiVO.sub.3), permanganic acid (HMnO.sub.4), sodium ferrate
(Na.sub.2FeO.sub.4), lithium cobaltate (LiCoO.sub.2), lithium
nickelate (LiNiO.sub.2), sodium yttrium oxide (NaYO.sub.2) sodium
zirconate (Na.sub.2ZrO.sub.3), lithium niobate (LiNbO.sub.3),
lithium molybdate (Li.sub.2MoO.sub.4), ruthenium acid
(H.sub.2RuO.sub.4), lithium rhodate (LiRhO.sub.2), lithium
palladate (Li.sub.2PdO.sub.3), lithium tantalate (LiTaO.sub.3),
sodium tungstate (Na.sub.2WO.sub.4), rhenium acid
(H.sub.2ReO.sub.4), potassium osmate (K.sub.2OsO.sub.4), potassium
iridate (KIrO.sub.3), sodium gallate (NaGaO.sub.2), sodium indium
oxide (NaInO.sub.2), sodium stannate (Na.sub.2SnO.sub.3), sodium
antimonate (NaSbO.sub.3) and sodium bismuthate (NaBiO.sub.3). These
compounds provide a better effect to the coating liquid used for
forming ultraviolet absorption coating.
[0049] Furthermore, the ultraviolet absorber is benzophenone
ultraviolet absorbers, benzimidazole-based ultraviolet absorber or
triazine-based ultraviolet absorber.
[0050] As a benzophenone ultraviolet absorber, it specifically
includes 2,4-dihydroxy benzophenone, 2, 2', 3 (or 4, 5,
6)-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone,
2,4-dihydroxy-T, 4'-dimethoxybenzophenone,
2-hydroxy-4-(octyloxy)benzophenone, etc.
[0051] As a benzimidazole ultraviolet absorber, it specifically
includes
2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV
absorber, commercial name is UV-234), 2-(5-chloro
(2H)-benzotriazole-2-yl)-4-methyl-6-(tert-butyl) phenol,
octyl-3-[3-t-4-hydroxy-5-[5-chloro-2H-benzotriazol-2-yl]
propionate, 2-(2H-benzotriazol-2-yl)-4,6-di-t-pentyl phenol,
2-(2-hydroxy-5-methylphenyl) benzotriazole,
2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalic
imide-methyl)-5-methylphenyl] benzotriazole,
2-(2-hydroxy-5-t-octylphenyl) benzotriazole,
2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,
methyl-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)
propionate, 2-(2H-benzotriazol-2-yl)-4,6-bis
(1-methyl-1-phenylethyl) phenol,
2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-te-
tramethylbutyl) phenol, etc.
[0052] As a triazine ultraviolet absorber, it specifically includes
2-[4-[(2-hydroxy-3-dodecyloxypropyl) oxy]-2-hydroxyphenyl]-4,6-bis
(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)
hexyl) oxy]-2-hydroxyphenyl]-4,6-bis
(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis
(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazin-
e, 2-(2-hydroxy-4-[1-octyl-carbethoxy] phenyl)-4,6-bis
(4-phenylphenyl)-1,3,5-triazine, TINUVIN477 (commercial name, from
Ciba Japan Company), etc.
[0053] The organic ultraviolet absorbers can absorb ultraviolet
light of wide wavelength range. In the present invention, the
ultraviolet absorbers may be used alone, or in a combination of two
or more according to the actual need.
[0054] The coating liquid is applied on the glass substrate to form
ultraviolet absorption coating, preparing ultraviolet absorption
glass. As shown in FIG. 1, the ultraviolet absorption glass
comprises glass substrate 1 and ultraviolet absorption coating 2,
where the ultraviolet absorption coating 2 is arranged on at least
one surface of the glass substrate 1. The ultraviolet absorption
coating 2 containing silicon dioxide (SiO.sub.2) and ultraviolet
absorber further comprises MOz used for storing and releasing
electrons that excited by ultraviolet lights in the ultraviolet
absorber, wherein O is oxygen, M is at least one element selected
from the group consisting of vanadium (V), manganese (Mn), iron
(Fe), cobalt (Co), nickel (Ni), yttrium (Y), zirconium (Zr),
niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh),
palladium (Pd), tantalum (Ta), tungsten (W), rhenium (Re), osmium
(Os), iridium (Ir), gallium (Ga), indium (In), stannum (Sn),
antimony (Sb) and bismuth (Bi), O is oxygen, and z is in a range of
1.ltoreq.z.ltoreq.4.
[0055] In the process where the ultraviolet absorber absorbs the UV
light, the ultraviolet absorber produces excited electrons and the
excited electrons are gradually stored in MOz
(1.ltoreq.z.ltoreq.4). The reaction equation (1) occurs:
MOz+ne.sup.-+nA.sup.+.fwdarw.AnMOz (1),
[0056] where O is oxygen, A is hydrogen or alkali metal, M is at
least one element selected from the group consisting of vanadium
(V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), yttrium
(Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru),
rhodium (Rh), palladium (Pd), tantalum (Ta), tungsten (W), rhenium
(Re), osmium (Os), iridium (Ir), gallium (Ga), indium (in), stannum
(Sn), antimony (Sb) and bismuth (Bi), z is in a range of
1.ltoreq.z.ltoreq.4, n is in a range of 1.ltoreq.n.ltoreq.2.
[0057] When there is no ultraviolet light, that is, the ultraviolet
absorber coating does not absorb the ultraviolet light, and the
excited electrons previously stored in MOz (1.ltoreq.z.ltoreq.4)
are released. The reaction equation (2) occurs:
AnMOz.fwdarw.MOz+ne.sup.-+nA.sup.+ (2).
[0058] Equation (2) is deemed to be a reverse reaction of equation
(1), where the notations are consistent with that in equation (1).
Therefore, the notations will not be illustrated in detail
herein.
[0059] At the same time, the electrons released in reaction (2)
diffuse to the surface of ultraviolet absorption glass, being
consumed by O.sub.2 of the air adsorbed on the surface of the
glass. The reaction equation (3) occurs:
O.sub.2+2e.sup.-.fwdarw.2O- (3).
[0060] It can be known from the reaction equation (1), (2) and (3)
that when the ultraviolet absorption coating 2 arranged on
ultraviolet absorption glass is exposed to the UV light, such as in
a sunny day, MOz will absorb and store the excited electrons. When
there is no UV light, such as at a dark night, MOz will gradually
release the electrons previously absorbed and stored in the
daytime. The process is equivalent to transferring the excited
electrons, thus avoiding the electrons accumulating and destroying
the silicon dioxide and ultraviolet absorber in the ultraviolet
absorption coating, not to cause discoloration or devitrification
to ultraviolet absorption coating and ultraviolet absorption
glass.
[0061] In practical applications, the MOz is at least one compound
selected from the group consisting of vanadium pentoxide
(VO.sub.5/2), manganese dioxide (MnO.sub.2), iron(III) oxide
(FeO.sub.3/2), cobalt oxide (II,III) (CoO.sub.4/3), nickel(II)
oxide (NiO), yttrium(III) oxide (YO.sub.3/2), zirconium dioxide
(ZrO.sub.2), niobium pentoxide (NbO.sub.5/2), molybdenum(VI) oxide
(MoO.sub.3), ruthenium dioxide (RuO.sub.2), rhodium(III) oxide
(RhO.sub.3/2), palladium(II) oxide (PdO), tantalum pentoxide
(TaO.sub.5/2), tungsten(VI) oxide (WO.sub.3), rhenium trioxide
(ReO.sub.3), osmium (VIII) oxide (OsO.sub.4), iridium dioxide
(IrO.sub.2), gallium(III) oxide (GaO.sub.3/2), indium (III) oxide
(InO.sub.3/2), tin(IV) oxide (SnO.sub.2), antimony pentoxide
(SbO.sub.5/2) and bismuth pentoxide (BiO.sub.5/2). These compounds
provide a better effect to the ultraviolet absorption glass
arranged with the coating.
[0062] The MOz listed above will reduce color difference
.DELTA.E*ab between the ultraviolet absorption glass and the glass
substrate 1. For example, using white float glass or green float
glass as the glass substrate 1 will achieve a color difference
.DELTA.E*ab between the ultraviolet absorption glass and the glass
substrate 1 under 2.0 (.DELTA.E*ab.ltoreq.2.0). In accordance with
practice, vanadium pentoxide (VO.sub.5/2), iron(III) oxide
(FeO.sub.3/2), cobalt oxide (II,III) (CoO.sub.4/3), yttrium(III)
oxide (YO.sub.3/2), niobium pentoxide (NbO.sub.5/2), rhodium(III)
oxide (RhO.sub.3/2), tantalum pentoxide (TaO.sub.5/2), gallium(III)
oxide (GaO.sub.3/2), indium (III) oxide (InO.sub.3/2), antimony
pentoxide (SbO.sub.5/2) and bismuth pentoxide (BiO.sub.5/2) are
written as V.sub.2O.sub.5, Fe.sub.2O.sub.3, Co.sub.3O.sub.4,
Y.sub.2O.sub.3, Nb.sub.2O.sub.5, Rh.sub.2O.sub.3, Ta.sub.2O.sub.5,
Ga.sub.2O.sub.3, In.sub.2O.sub.3, Sb.sub.2O.sub.5 and
Bi.sub.2O.sub.5, being consistent with the form of MOz without
changing its actual meaning.
[0063] Furthermore, the ultraviolet absorber is benzophenone
ultraviolet absorber, benzimidazole ultraviolet absorber or
triazine ultraviolet absorber.
[0064] As a benzophenone ultraviolet absorber, it specifically
includes 2,4-dihydroxy benzophenone, 2, 2', 3 (or
4/5/6)-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone,
2,4-dihydroxy-2', 4'-dimethoxybenzophenone,
2-hydroxy-4-(octyloxy)benzophenone, etc.
[0065] As a benzimidazole ultraviolet absorber, it specifically
includes
2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV
absorber, commercial name is UV-234), 2-(5-chloro
(2H)-benzotriazole-2-yl)-4-methyl-6-(tert-butyl) phenol,
octyl-3-[3-t-4-hydroxy-5-[5-chloro-2H-benzotriazol-2-yl]
propionate, 2-(2H-benzotriazol-2-yl)-4,6-di-t-pentyl phenol,
2-(2-hydroxy-5-methylphenyl) benzotriazole,
2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalic
imide-methyl)-5-methylphenyl] benzotriazole,
2-(2-hydroxy-5-t-octylphenyl) benzotriazole,
2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,
methyl-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)
propionate, 2-(2H-benzotriazol-2-yl)-4,6-bis
(1-methyl-1-phenylethyl) phenol,
2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-te-
tramethylbutyl) phenol, etc.
[0066] As a triazine ultraviolet absorber, it specifically includes
2-[4-[(2-hydroxy-3-dodecyloxypropyl) oxy]-2-hydroxyphenyl]-4,6-bis
(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)
hexyl) oxy]-2-hydroxyphenyl]-4,6-bis
(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis
(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazin-
e, 2-(2-hydroxy-4-[1-octyl-carbethoxy] phenyl)-4,6-bis
(4-phenylphenyl)-1,3,5-triazine, TINUVIN477 (commercial name, from
Ciba Japan Company), etc.
[0067] The organic ultraviolet absorbers can absorb ultraviolet
light of wide wavelength range. In the present invention, the
ultraviolet absorbers may be used alone, or in a combination of two
or more according to the actual need.
[0068] In the present invention, silicon dioxide is used for
improving hardness and adhesion to the glass substrate 1 of the
ultraviolet absorption coating 2 which is formed by the coating
liquid, thereby ensuring high durability of the ultraviolet
absorption coating 2. Preferably, in an ultraviolet absorption
coating 2, a molar ratio of MOz to silicon dioxide is in a range of
1/300-1/100. More preferably, in the ultraviolet absorption coating
2, a molar ratio of MOz to silicon dioxide is in a range of
1/180-1/120.
[0069] In the present invention, an ultraviolet absorber absorbs
ultraviolet light and blocks the UV light coming into the vehicle
or the house, avoiding damage to people and aging of the
decoration. Preferably, in an ultraviolet absorption coating, a
molar ratio of MOz to ultraviolet absorber is in a range of
1/20-1/10. More preferably, in the ultraviolet absorption coating
2, a molar ratio of MOz to silicon dioxide is in a range of
1/18-1/12.
[0070] A coating liquid used for forming an ultraviolet absorption
coating and an ultraviolet absorption glass arranged with the
ultraviolet absorption coating are described above in detail.
Furthermore, the present invention provides a method for preparing
the ultraviolet absorption glass, comprising the following
steps.
[0071] Step 1: providing silane compound and AxMOy as raw material,
providing deionized water and at least one alcohol as a solvent,
stirring and ultrasonically dispersing the raw material and
solvent, wherein A is hydrogen or an alkali metal, O is oxygen, M
is at least one element selected from the group consisting of
vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni),
yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo),
ruthenium (Ru), rhodium (Rh), palladium (Pd), tantalum (Ta),
tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gallium
(Ga), indium (In), tin (Sn), antimony (Sb) and bismuth (Bi), x is
in a range of 1.ltoreq.x.ltoreq.2, y is in a range of
1.ltoreq.y.ltoreq.4.
[0072] The silane compound is at least one compound selected from
but not limited to the group consisting of tetramethoxysilane,
tetraethoxysilane, trimethoxysilane, triethoxysilane and
dimethoxydimethylsilane. Any other colloid substance that produces
partially hydrolyzed condensate via hydrolysis or a series of
reaction can be selected.
[0073] As a solvent, the alcohol may be but not limited to ethanol
and isopropanol, other alcohols can also be selected according to
actual need.
[0074] AxMOy is preferably at least one compound selected from the
group consisting of lithium vanadate (LiVO.sub.3), permanganic acid
(HMnO.sub.4), sodium ferrate (Na.sub.2FeO.sub.4), lithium cobaltate
(LiCoO.sub.2), lithium nickelate (LiNiO.sub.2), sodium yttrium
oxide (NaYO.sub.2) sodium zirconate (Na.sub.2ZrO.sub.3), lithium
niobate (LiNbO.sub.3), lithium molybdate (Li.sub.2MoO.sub.4),
ruthenium acid (H.sub.2RuO.sub.4), lithium rhodate (LiRhO.sub.2),
lithium palladate (Li.sub.2PdO.sub.3), lithium tantalate
(LiTaO.sub.3), sodium tungstate (Na.sub.2WO.sub.4), rhenium acid
(H.sub.2ReO.sub.4), potassium osmate (K.sub.2OsO.sub.4), potassium
iridate (KIrO.sub.3), sodium gallate (NaGaO.sub.2), sodium indium
oxide (NaInO.sub.2), sodium stannate (Na.sub.2SnO.sub.3), sodium
antimonate (NaSbO.sub.3) and sodium bismuthate (NaBiO.sub.3).
[0075] Step 2: after the step of stirring and ultrasonically
dispersing, conducting a hydrolysis reaction and a condensation
reaction between the raw material and solvent to produce a colloid
B containing silicon dioxide in a form of a partially hydrolyzed
condensate.
[0076] As a matrix of the final ultraviolet absorption coating,
silicon dioxide improves hardness and adhesion to the glass
substrate of the ultraviolet absorption coating which is formed by
the coating liquid, thereby ensuring high durability of the
ultraviolet absorption coating.
[0077] Step 3: adding an ultraviolet absorber and a silane additive
to the colloid B while stirring to dissolve the ultraviolet
absorber, then obtaining a coating liquid C used for forming an
ultraviolet absorption coating.
[0078] The silane additive is at least one compound selected from
the group consisting of
N-[3-(trimethoxysilyl)propyl]ethylenediamine,
[3-(methacryloyloxy)propyl]trimethoxysilane,
[3-(2-aminoethyl)aminopropyl] trimethoxysilane and
[3-(methacryloyloxy)propyl]triethoxysilane.
[0079] The ultraviolet absorber is benzophenone ultraviolet
absorber, benzimidazole ultraviolet absorber or triazine
ultraviolet absorber. These three ultraviolet absorbers have been
described in detail in the above description, it is not further
described herein.
[0080] Step 4: preparing a glass substrate, applying the coating
liquid C uniformly on at least one surface of the glass
substrate.
[0081] The glass substrate is preferably but not limited to a white
float glass or a green float glass. Any glass sheet prepared by
other methods that meet the requirements will be selected as the
glass substrate of the present invention.
[0082] At the same time, the coating liquid C can be uniformly
applied on the glass substrate in different ways, such as spraying,
wiping, flow coating, brushing and dipping that optionally combines
with ultrasound, centrifugation or rotation techniques. Since the
coating technique is known in the art, it is not further described
herein.
[0083] Step 5: drying the coating liquid C at a temperature of
100.degree. C.-200.degree. C. to form an ultraviolet absorption
coating containing MOz on a surface of the glass substrate, O is
oxygen, M is at least one element selected from the group
consisting of vanadium (V), manganese (Mn), iron (Fe), cobalt (Co),
Nickel (Ni), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum
(Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), tantalum (Ta),
tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gallium
(Ga), indium (in), tin (Sn), antimony (Sb) and bismuth (Bi), z is
in a range of 1.ltoreq.z.ltoreq.4, thereby obtaining an ultraviolet
absorption glass.
[0084] The MOz is at least one compound selected from the group
consisting of vanadium pentoxide (VO.sub.5/2), manganese dioxide
(MnO.sub.2), iron(III) oxide (FeO.sub.3/2), cobalt oxide (II,III)
(CoO.sub.4/3), nickel(II) oxide (NiO), yttrium(III) oxide
(YO.sub.3/2), zirconium dioxide (ZrO.sub.2), niobium pentoxide
(NbO.sub.5/2), molybdenum(VI) oxide (MoO.sub.3), ruthenium dioxide
(RuO.sub.2), rhodium(III) oxide (RhO.sub.3/2), palladium(II) oxide
(PdO), tantalum pentoxide (TaO.sub.5/2), tungsten(VI) oxide
(WO.sub.3), rhenium trioxide (ReO.sub.3), osmium (VIII) oxide
(OsO.sub.4), iridium dioxide (IrO.sub.2), gallium(III) oxide
(GaO.sub.3/2), indium (III) oxide (InO.sub.3/2), tin(IV) oxide
(SnO.sub.2), antimony pentoxide (SbO.sub.5/2) and bismuth pentoxide
(BiO.sub.5/2).
[0085] The step of drying the coating liquid C is conducted for 30
to 120 minutes. It is understood that the time for drying depends
on the different coating liquid C, so that the time for drying is
determined according to the actual conditions.
EXAMPLES
[0086] Further description of the present invention will be
illustrated, which combined with embodiments. It will be understood
that the embodiments are illustrative and that the invention scope
is not so limited.
[0087] As the compounds MOz are similar in reaction mechanism,
tungsten trioxide (WO.sub.3) is used as an example to explain the
present invention. Other MOz compounds will not be illustrated in
detail herein.
Example 1
[0088] 10 g of TEOS and 0.1 g of sodium tungstate
(Na.sub.2WO.sub.4) were used as raw material, while ethanol,
isopropanol and deionized water were used as solvent. The raw
material and solvent were stirred and ultrasonically dispersed.
After the step of stirring and ultrasonically dispersing, a
hydrolysis reaction and a condensation reaction were conducted
between the raw material and solvent to produce a colloid B
containing silicon dioxide in a form of a partially hydrolyzed
condensate. To 20 g of colloid B, 1.2 g of UV absorber
2,4-dihydroxy-T, 4'-dimethoxybenzophenone and 0.02 g of KH560
(purchased from Nanjing Shuguang Company) were added while stirring
to dissolve the UV absorber. A stirring was continued for 2 hours
to obtain a coating liquid C used for forming an ultraviolet
absorption coating.
[0089] A white float glass (FUYAO 3.2C) was provided as a glass
substrate. The white float glass has a thickness of 3.2 mm, a color
of L*=95.67, a*=-1.53, b*=1.28, a size of 150 mm.times.150 mm, and
a UV-blocking rate of 31.67%. 2.3 g of the coating liquid C were
uniformly applied on the surface of the glass substrate, and then
dried at 150.degree. C. for 1 hour to obtain an ultraviolet
absorption glass arranged with the ultraviolet absorption coating,
where a molar ratio of tungsten trioxide (WO.sub.3) to silicon
dioxide (SiO.sub.2) is 1:158.7, a molar ratio of tungsten trioxide
(WO.sub.3) to the ultraviolet absorber is 1:16.1. The ultraviolet
absorption glass was evaluated according to the performance
evaluation method described below, and the evaluation results are
shown in Table 1.
[0090] Performance Evaluation
[0091] (1) UV-blocking rate: a transmission spectrum of a
wavelength of 250 nm-2500 nm was generated by using a
spectrophotometer (Mode: Perkin Elmer Lambda 950).
[0092] Lta was calculated according to ASTM E308-01 standard. Tuv
and Te were calculated according to ISO9050-2003(E) standard. Tir
was calculated according to TL957-2011 standard. Tuv was a
calculated value of UV transmittance of a wavelength of 300 nm-380
nm. UV-blocking rate=100%-UV transmittance. UV transmittance was an
average value calculated from 5 points of one sample.
[0093] (2) Color difference between ultraviolet absorption glass
and glass substrate .DELTA.E*ab: a transmission spectrum of a
wavelength of 250 nm-2500 nm was generated by using a
spectrophotometer (Mode: Perkin Elmer Lambda 950).
[0094] L*, a* and b* were calculated according to CIE 1976
standard: average values of L*, a* and b* calculated from 5 points
of one glass substrate were denoted by L*1, a*1, b*1, respectively;
average value of L*, a* and b* calculated from 5 points of one
ultraviolet absorption glass were denoted by L*2, a*2, b*2,
respectively. Lightness difference, color difference and total
color difference .DELTA.E*ab were given by
Lightness difference:.DELTA.L*=L*1-L*2
Color difference:.DELTA.a*=a*1-a*2
.DELTA.b*=b*1-b*2
Total color
difference:.DELTA.E*ab=[(.DELTA.L*).sup.2+(.DELTA.a*).sup.2+(.DELTA.b*).s-
up.2].sup.1/2.
[0095] (3) Weather resistance test: the glass substrate and the
ultraviolet absorption glass were simultaneously put into the xenon
lamp aging test apparatus (Model: CI4000, United States) subjected
to the weather resistance test under the following conditions:
cycle: drying for 102 min and raining for 18 min; wavelength:
300-400 nm; radiation intensity: (60.+-.2) w/m.sup.2, black board
temperature: (65.+-.3.degree.) C., tank temperature:
(38.+-.3.degree.) C., relative humidity: (50.+-.10)%, testing time:
1000 hours. After the weather resistance test, the samples were
evaluated by step (1) and (2), UV-blocking rate and color
difference .DELTA.E*ab between the ultraviolet absorption glass and
the glass substrate were calculated.
Example 2
[0096] A green float glass (FUYAO 3.2G) was provided as a glass
substrate. The green float glass has a thickness of 3.2 mm, a color
of L*=93.02, a*=-4.57, b*=1.62, a size of 150 mm.times.150 mm, and
a UV-blocking rate of 59.11%. The glass substrate was treated in
the same manner that of Example 1 to produce an ultraviolet
absorption glass arranged with the ultraviolet absorption coating.
The ultraviolet absorption glass was evaluated according to the
performance evaluation method described in Example 1, and the
evaluation results are shown in Table 1.
Example 3
[0097] A green float glass (FUYAO 3.2SG) was provided as a glass
substrate. The green float glass has a thickness of 3.2 mm, a color
of L*=89.47, a*=-7.23, b*=4.25, a size of 150 mm.times.150 mm, and
a UV-blocking rate of 76.49%. The glass substrate was treated in
the same manner that of Example 1 to produce an ultraviolet
absorption glass arranged with the ultraviolet absorption coating.
The ultraviolet absorption glass was evaluated according to the
performance evaluation method described in Example 1, and the
evaluation results are shown in Table 1.
Example 4
[0098] A white float glass (FUYAO 3.2C) was provided as a glass
substrate. The white float glass has a thickness of 3.2 mm, a color
of L*=95.53, a*=-1.13, b*=0.18, a size of 150 mm.times.150 mm, and
a UV-blocking rate of 31.67%. In this embodiment, the glass
substrate is treated without applying the ultraviolet absorption
coating liquid of the present invention (deemed as a common glass).
The common glass was evaluated according to the performance
evaluation method described in Example 1, and the evaluation
results are shown in Table 1.
Example 5
[0099] A green float glass (FUYAO 3.2G) was provided as a glass
substrate. The green float glass has a thickness of 3.2 mm, a color
of L*=92.98, a*=-4.15, b*=0.61, a size of 150 mm.times.150 mm, and
a UV-blocking rate of 59.11%. In this embodiment, the glass
substrate is treated without applying the ultraviolet absorption
coating liquid of the present invention (deemed as a common glass).
The common glass was evaluated according to the performance
evaluation method described in Example 1, and the evaluation
results are shown in Table 1.
Example 6
[0100] A green float glass (FUYAO solar 3.2SG) was provided as a
glass substrate. The green float glass has a thickness of 3.2 mm, a
color of L*=89.33, a*=-6.67, b*=3.16, a size of 150 mm.times.150
mm, and a UV-blocking rate of 76.49%. In this embodiment, the glass
substrate is treated without applying the ultraviolet absorption
coating liquid of the present invention (deemed as a common glass).
The common glass was evaluated according to the performance
evaluation method described in Example 1, and the evaluation
results are shown in Table 1.
TABLE-US-00001 TABLE 1 Performance evaluation results of the
ultraviolet absorption glass of Example 1-6 Example 1 Example 2
Example 3 Example 4 Example 5 Example 6 Lta 89.25% 82.99% 75.24%
88.86% 82.86% 74.89% Tuv 0.15% 0.55% 0.28% 68.33% 40.89% 23.51% Te
79.06% 60.68% 47.46% 81.93% 62.84% 48.85% Tir 77.23% 47.36% 30.02%
76.59% 47.16% 29.83% L* 95.67 93.02 89.47 95.53 92.98 89.33 a*
-1.53 -4.57 -7.23 -1.13 -4.15 -6.77 b* 1.28 1.62 4.25 0.18 0.61
3.16 Before.sup.1* UV-blocking rate 99.85% 99.45% 99.72% 31.67%
59.11% 76.49% decision .smallcircle. .smallcircle. .smallcircle. x
x x .DELTA.E*ab 1.18 1.09 1.19 -- -- -- decision .smallcircle.
.smallcircle. .smallcircle. -- -- -- After.sup.2* UV-blocking rate
99.83% 99.45% 99.70% 31.68% 59.10% 76.49% decision .smallcircle.
.smallcircle. .smallcircle. x x x .DELTA.E*ab 1.22 1.11 1.24 0.01
0.02 0.02 decision .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. Note: Before.sup.1*:
before weather resistance test; After.sup.2*: after weather
resistance test.
[0101] In the above table, Lta is visible light transmittance of a
wavelength of 380 nm-780 nm. Tuv is UV transmittance of a
wavelength of 300 nm-380 nm. Te is total solar energy transmittance
of a wavelength of 300 nm-2500 nm. Tir is infrared ray
transmittance of a wavelength of 780 nm-2500 nm. UV-blocking
rate=100%-UV transmittance, i.e. UV-blocking rate=100%-Tuv. The
notation "o" represents "pass", the notation "x" represents "fail",
and the notation "A" represents approach to a boundary value.
[0102] It can be seen from table 1 that the coating liquid used for
forming ultraviolet absorption coating of the present invention can
be used for various glass substrates, such as white float glass,
green float glass, etc. An ultraviolet absorption coating forms on
the surface of the glass substrate to bring a better UV-blocking
rate and weather resistance to ultraviolet absorption glass.
Example 7
[0103] 10 g of TEOS and 0.099 g of sodium tungstate
(Na.sub.2WO.sub.4) were used as raw material, while ethanol,
isopropanol and deionized water were used as solvent. The raw
material and solvent were stirred and ultrasonically dispersed.
After the step of stirring and ultrasonically dispersing, a
hydrolysis reaction and a condensation reaction were conducted
between the raw material and solvent to produce a colloid B
containing silicon dioxide in a form of partially hydrolyzed
condensate. To 20 g of colloid B, 1.201 g of UV absorber
2,4-dihydroxy-2', 4'-dimethoxybenzophenone and 0.02 g of KH560
(purchased from Nanjing Shuguang Company) were added while stirring
to dissolve the UV absorber. A stirring was continued for 2 hours
to obtain a coating liquid C used for forming an ultraviolet
absorption coating.
[0104] A green float glass (FUYAO 3.2G) was provided as a glass
substrate. The green float glass has a thickness of 3.2 mm, a size
of 150 mm.times.150 mm, and a UV-blocking rate of 59.11%. 2.3 g of
the coating liquid C were uniformly applied on the surface of the
glass substrate, and then dried at 150.degree. C. for 1 hour to
obtain an ultraviolet absorption glass arranged with the
ultraviolet absorption coating, where a molar ratio of tungsten
trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) is 1:158.6, a
molar ratio of tungsten trioxide (WO.sub.3) to the ultraviolet
absorber is 1:16.1. The ultraviolet absorption glass was evaluated
according to the performance evaluation method described in Example
1, and the evaluation results are shown in Table 2.
Example 8
[0105] The embodiment was prepared in the manner similar to that of
Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was
added in an amount sufficient to adjust the molar ratio of tungsten
trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of
1:350. An ultraviolet absorption glass arranged with the
ultraviolet absorption coating was obtained. The ultraviolet
absorption glass was evaluated according to the performance
evaluation method described in Example 1, and the evaluation
results are shown in Table 2.
Example 9
[0106] The embodiment was prepared in the manner similar to that of
Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was
added in an amount sufficient to adjust the molar ratio of tungsten
trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of
1:300. An ultraviolet absorption glass arranged with the
ultraviolet absorption coating was obtained. The ultraviolet
absorption glass was evaluated according to the performance
evaluation method described in Example 1, and the evaluation
results are shown in Table 2.
Example 10
[0107] The embodiment was prepared in the manner similar to that of
Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was
added in an amount sufficient to adjust the molar ratio of tungsten
trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of
1:180. An ultraviolet absorption glass arranged with the
ultraviolet absorption coating was obtained. The ultraviolet
absorption glass was evaluated according to the performance
evaluation method described in Example 1, and the evaluation
results are shown in Table 2.
Example 11
[0108] The embodiment was prepared in the manner similar to that of
Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was
added in an amount sufficient to adjust the molar ratio of tungsten
trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of
1:120. An ultraviolet absorption glass arranged with the
ultraviolet absorption coating was obtained. The ultraviolet
absorption glass was evaluated according to the performance
evaluation method described in Example 1, and the evaluation
results are shown in Table 2.
Example 12
[0109] The embodiment was prepared in the manner similar to that of
Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was
added in an amount sufficient to adjust the molar ratio of tungsten
trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of
1:100. An ultraviolet absorption glass arranged with the
ultraviolet absorption coating was obtained. The ultraviolet
absorption glass was evaluated according to the performance
evaluation method described in Example 1, and the evaluation
results are shown in Table 2.
Example 13
[0110] The embodiment was prepared in the manner similar to that of
Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was
added in an amount sufficient to adjust the molar ratio of tungsten
trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of
1:80. An ultraviolet absorption glass arranged with the ultraviolet
absorption coating was obtained. The ultraviolet absorption glass
was evaluated according to the performance evaluation method
described in Example 1, and the evaluation results are shown in
Table 2.
Example 14
[0111] The embodiment was prepared in the manner similar to that of
Example 7, except that the ultraviolet absorber was added in an
amount sufficient to adjust the molar ratio of tungsten trioxide
(WO.sub.3) to ultraviolet absorber to a value of 1:25. An
ultraviolet absorption glass arranged with the ultraviolet
absorption coating was obtained. The ultraviolet absorption glass
was evaluated according to the performance evaluation method
described in Example 1, and the evaluation results are shown in
Table 2.
Example 15
[0112] The embodiment was prepared in the manner similar to that of
Example 7, except that the ultraviolet absorber was added in an
amount sufficient to adjust the molar ratio of tungsten trioxide
(WO.sub.3) to ultraviolet absorber to a value of 1:20. An
ultraviolet absorption glass arranged with the ultraviolet
absorption coating was obtained. The ultraviolet absorption glass
was evaluated according to the performance evaluation method
described in Example 1, and the evaluation results are shown in
Table 2.
Example 16
[0113] The embodiment was prepared in the manner similar to that of
Example 7, except that the ultraviolet absorber was added in an
amount sufficient to adjust the molar ratio of tungsten trioxide
(WO.sub.3) to ultraviolet absorber to a value of 1:18. An
ultraviolet absorption glass arranged with the ultraviolet
absorption coating was obtained. The ultraviolet absorption glass
was evaluated according to the performance evaluation method
described in Example 1, and the evaluation results are shown in
Table 2.
Example 17
[0114] The embodiment was prepared in the manner similar to that of
Example 7, except that the ultraviolet absorber was added in an
amount sufficient to adjust the molar ratio of tungsten trioxide
(WO.sub.3) to ultraviolet absorber to a value of 1:12. An
ultraviolet absorption glass arranged with the ultraviolet
absorption coating was obtained. The ultraviolet absorption glass
was evaluated according to the performance evaluation method
described in Example 1, and the evaluation results are shown in
Table 2.
Example 18
[0115] The embodiment was prepared in the manner similar to that of
Example 7, except that the ultraviolet absorber was added in an
amount sufficient to adjust the molar ratio of tungsten trioxide
(WO.sub.3) to ultraviolet absorber to a value of 1:10. An
ultraviolet absorption glass arranged with the ultraviolet
absorption coating was obtained. The ultraviolet absorption glass
was evaluated according to the performance evaluation method
described in Example 1, and the evaluation results are shown in
Table 2.
Example 19
[0116] The embodiment was prepared in the manner similar to that of
Example 7, except that the ultraviolet absorber was added in an
amount sufficient to adjust the molar ratio of tungsten trioxide
(WO.sub.3) to ultraviolet absorber to a value of 1:6. An
ultraviolet absorption glass arranged with the ultraviolet
absorption coating was obtained. The ultraviolet absorption glass
was evaluated according to the performance evaluation method
described in Example 1, and the evaluation results are shown in
Table 2.
TABLE-US-00002 TABLE 2 Performance evaluation results of the
ultraviolet absorption glass of Example 7-19 Before weather
resistance test After weather resistance test UV-blocking rate
decision .DELTA.E*ab decision UV-blocking rate decision .DELTA.E*ab
decision Example 7 99.44% .smallcircle. 1.1 .smallcircle. 99.38%
.smallcircle. 1.12 .smallcircle. Example 8 99.49% .smallcircle.
0.75 .smallcircle. 98.11% x 5.77 x Example 9 99.40% .smallcircle.
0.77 .smallcircle. 99.03% .smallcircle. 1.39 .DELTA. Example 10
99.43% .smallcircle. 0.80 .smallcircle. 99.19% .smallcircle. 1.16
.smallcircle. Example 11 99.56% .smallcircle. 1.14 .smallcircle.
99.56% .smallcircle. 1.21 .smallcircle. Example 12 99.48%
.smallcircle. 1.18 .smallcircle. 99.47% .smallcircle. 1.36 .DELTA.
Example 13 99.44% .smallcircle. 2.12 x 99.42% .smallcircle. 3.14 x
Example 14 99.81% .smallcircle. 0.87 .smallcircle. 99.43%
.smallcircle. 2.10 x Example 15 99.75% .smallcircle. 0.80
.smallcircle. 99.50% .smallcircle. 1.39 .DELTA. Example 16 99.72%
.smallcircle. 0.81 .smallcircle. 99.50% .smallcircle. 1.17
.smallcircle. Example 17 99.22% .smallcircle. 0.77 .smallcircle.
99.00% .smallcircle. 1.10 .smallcircle. Example 18 99.10% .DELTA.
0.77 .smallcircle. 99.02% .DELTA. 0.97 .smallcircle. Example 19
98.13% x 0.72 .smallcircle. 97.91% x 0.93 .smallcircle.
[0117] Compared Example 7 with 8-13, it can be seen from table 2
that a molar ratio of WO.sub.3 to silicon dioxide in a range of
1/300-1/100, preferably 1/180-1/120 will bring a better UV-blocking
rate and weather resistance to ultraviolet absorption glass.
[0118] Compared Example 7 with 14-19, it can be seen from table 2
that a molar ratio of WO.sub.3 to ultraviolet absorber in a range
of 1/20-1/10, preferably 1/18-1/12 will bring a better UV-blocking
rate and weather resistance to ultraviolet absorption glass.
Example 20
[0119] The embodiment was prepared in the manner similar to that of
Example 7, except that sodium tungstate (Na.sub.2WO.sub.4) and the
ultraviolet absorber were not added. A coating glass arranged with
a coating was obtained. The coating glass was evaluated according
to the performance evaluation method described in Example 1, and
the evaluation results are shown in Table 3.
Example 21
[0120] The embodiment was prepared in the manner similar to that of
Example 7, except that the ultraviolet absorber was not added. A
coating glass arranged with a coating was obtained. The coating
glass was evaluated according to the performance evaluation method
described in Example 1, and the evaluation results are shown in
Table 3.
TABLE-US-00003 TABLE 3 Performance evaluation results of the glass
obtained from Example 20-21 Lta Tuv Te Tir L* a* b* Example 20
83.35% 41.42% 63.05% 47.10% 93.20 -4.18 0.55 Example 21 83.57%
42.01% 62.82% 47.12% 93.29 -4.22 0.61
[0121] It can be seen from table 3 that a coating glass without
adding sodium tungstate (Na.sub.2WO.sub.4) and ultraviolet absorber
(i.e. the coating contains no WO.sub.3 and ultraviolet absorber)
has no UV-blocking and IR-blocking function. Similarly, the coating
glass adding Na.sub.2WO.sub.4 without the ultraviolet absorber
(i.e. the coating contains WO.sub.3 but no ultraviolet absorber)
has no UV-blocking and IR-blocking function. It indicates that the
WO.sub.3 blocks neither ultraviolet light nor infrared ray, but
plays an important role in storing and releasing the electrons
excited by the UV light in the ultraviolet absorber.
[0122] While the present invention has been described with
reference to particular embodiments, it will be understood that the
embodiments are illustrative and that the invention scope is not so
limited. Alternative embodiments of the present invention will
become apparent to those having ordinary skill in the art to which
the present invention pertains. Such alternate embodiments are
considered to be encompassed within the scope of the present
invention. Accordingly, the scope of the present invention is
described by the appended claims and is supported by the foregoing
description.
* * * * *